In the Laboratory
Synthesis of Molybdenum–Molybdenum Quadruple Bonds W
A Multistep Advanced Synthesis Laboratory Experiment
Laura E. Pence,* Amy M. Weisgerber, and Florence A. Maounis
Department of Chemistry, University of Hartford, West Hartford, CT 06117
The concept of quadruple bonds formed between tran-
sition metal atoms is often not encountered until students
are juniors or seniors, and it is rarely reinforced by laboratory
experience, owing to a paucity of easily reproducible experiments
at the advanced level. We describe an inorganic experiment
that focuses on the formation of the quadruple bond and the
substitution chemistry of the assembled dimetal unit for the
relatively unfamiliar second-row transition element, molyb-
denum. The intense and varied colors of the products dem-
onstrate the influence of π-donor, σ-donor, and π-acceptor
ligands on the energies of the frontier molecular orbitals; shifts
in orbital energies alter the wavelength of the δ– δ * transition
in the visible region. The experiment requires students to
learn inert atmosphere techniques, but affordable methods
are presented as alternatives to glove boxes and vacuum lines.
This multistep inorganic experiment is appropriate for
an advanced synthetic or integrated laboratory course and is
designed to include common aspects of industrial and aca-
demic working environments. By carrying out three sequential
reactions in which the product of one reaction is the starting
material for the next, students are introduced to the complex
process of chemical research, which will ease the transition that
they make from single-step introductory laboratory experiments
to their postgraduate experiences. The molybdenum experiment
also may be adapted for a team or “research group” of students
who collaborate on the final results. Because up to nine
tertiary phosphine complexes may be made in the final step,
students can work on parallel syntheses while making different
products. Spectroscopic data for the final products may be
compiled by the group to give a greater understanding of
features that vary or remain constant among closely related
compounds. The teamwork skills fostered by collaboration
are important to the students’ professional futures.
An advanced synthetic experiment should challenge
students with new techniques and new responsibilities. The
sequence of reactions in this experiment achieves both of these
goals. In the first reaction (Scheme I), which is used to prepare
the metal–metal bonded compound Mo2(O2CCH3)4, students
learn proper procedures for handling the toxic substance
Mo(CO)6 as well as how handle compressed gases and how
to run a reaction under a positive pressure of nitrogen.
H3 H3
C C
CO O O O O
OC CO Step 1
2 Mo Mo Mo
OC CO O O O O
CO
C C
H3 H3
Step 2
Cl PR3 Cl Cl 4-
PR3 Cl Step 3 Cl Cl
Mo Mo Mo Mo
R3P Cl Cl PR3 Cl Cl Cl Cl
Scheme I
404 Journal of Chemical Education • Vol. 76 No. 3 March 1999 • JChemEd.chem.wisc.edu
HCl gas is required for the preparation of [Mo2Cl8] 4{ in step 2,
but rather than purchasing a tank of the corrosive gas, students
learn to generate the gas through the dropwise addition of
H2SO4 to HCl. This procedure has the merits of not damaging
regulators, and it allows the residual acids to be discarded
down the drain after neutralization and dilution. The reaction
to form the phosphine complex, Mo2Cl4(PR3)4, in step 3 builds
on several techniques learned in step 1. If proper handling
techniques were acquired in the first reaction, then dispensing
liquid phosphines without polluting the laboratory with the
pungent stench of the chemicals will be easy. Unlike the first
reaction, which may be assembled in air, the third reaction
must be assembled under an inert atmosphere and requires
deoxygenated solvent to prevent oxidation of the phosphine.
Therefore, the students gain experience with glove-bag
manipulation and learn the techniques of keeping a system free
of air. The final molybdenum–phosphine compound is relatively
unreactive in the solid state but decomposes in solution.
Therefore samples for UV-vis or NMR analysis must also be
prepared by using deoxygenated solvents in a glove bag.
We have tried to minimize the cost of implementing this
new experiment. Most academic laboratories will have access to
N2/Ar gas regulators, bubblers, 1-mL plastic or glass syringes,
and most common glassware. The pressure-equalizing dropping
funnels for the HCl gas generation apparatus may be obtained
from Ace Glass if necessary. If a still is not available for dis-
tillation of methanol under an inert gas, then the solvent may
be deoxygenated by purging with Ar or N2 for 20 minutes
before use. The required chemicals that are not typically
found in academic laboratories may be obtained from
Aldrich, including the molybdenum hexacarbonyl, Mo(CO)6,
used in the first step and the tertiary phosphines, PR3, used in
step 3. In our experiments we tested PEt3, PMePh2, and PEtPh2;
PMe3, PEt2Ph, PMe2Ph, P(n-Pr)3, P(n-Bu)3, and P(OMe)3
are other phosphines whose molybdenum complexes are
known.
Students filling out anonymous evaluations at the end
of Advanced Synthesis enthusiastically indicated that the
experiment should be repeated in subsequent years. An infor-
mal survey indicated that the array of colors was one of the
most appealing components of the experiment, although the
students also displayed an avid interest in the variety of
reactions and techniques that they learned. By carrying out
three sequential reactions on the molybdenum system, students
gained a better appreciation of the reactivity of the compounds
in this field of chemistry compared to the experience obtained
in a more common single-step experiment. The differing time
scales and temperature requirements of the three reactions
allowed students to appreciate the difference in the energy
W Supplementary materials for this article are available on JCE
Online at http://JChemEd.chem.wisc.edu/Journal/issues/1999/
Mar/abs404.html.
*Corresponding author. Email: lpence@mail.hartford.edu.
 In the Laboratory

barrier to metal–metal bond formation compared to ligand and ligand type. The wide variety of techniques presented in
substitution. The vivid colors of the three products, bright this set of reactions combined with exposure to an unusual
yellow, purple, and royal blue, were visual indications of the set of compounds makes this a valuable experiment that
relationships among color, electronic spectrum, orbital energies, occupies a formerly unfilled niche in our curriculum.

JChemEd.chem.wisc.edu • Vol. 76 No. 3 March 1999 • Journal of Chemical Education 405